Process for treatment of hydrocarbons



Feb. 17, 1942. w. A. scHuLzE PROCESS FOR TREATMENT OF HYDROCARBONS Filed Jan. 3, 1939 'lvl w o zomomo o W Mr owwmmazou 55D: Q IT mzjow SNE v\ 1 tz: wzrmm IXI 4 n lNvEN'roR WALTER A. ScHuLzE ATTORNEY Puentes Feb. 1v, 1942 UNITED STATES PATENT oF-Flcs 2.21am i raocsss roa saumur or maol cannons wsltaschumnuuesvme.okla,mmito Phillipsretroleumcompannaoorponthno! Delaware application :mum s, icas, sensi No. 249,14

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through conduit am a irscuohauhg'nita: "The f overhead m the :mamans uitstekend! r; through conduit I having a branch" l forcon# This invention relates to the" art of treating hydrocarbons in the vapor'form with-solid contact catalysts and `relates more particularly to the treatment of the lower boiling distillates produced by cracking heavier hydrocarbon oil mixtures and to vapor recovery and polymerized gasoline stocks though the process is applicable also to the treatment of similar distillates produced in the straight run distillation of petroleums, to natural gasoline and to'other hydrocarbon materials.

In a more speciilc sense the invention has reference to a process for treating suchmotot fuel stocks to reduce their sulfur content, improve their antiknock characteristics and produce other desirable renning effects.

Many processes have been suggested heretofore for improving motor fuel stocks by contact with catalysts. In all of these processes, however,` the catalyst becomes poisoned after a time by certain vbodies either present in the vapors or formed by reaction between the catalyst and the hydrocarbon vapors and/or impurities in the vapors. I' have found that the rate oi' poisoning of these catalysts varies greatly with the various gasoline stocks, some o! them reducing` the catalyst activity to an uneconomic level within a period of several hours or less. Highly cracked gasolines and pressure distillates, polymerised gasoline stocks and vapor recovery gasolines are especialy bad in this connection.

An object of my invention is a process for. treating these hydrocarbon vapors which rapidly poison contact catalysts, such vapors being referred to herein under the general term of of the various "potentialf' `poisoningj agefrits"in cracked gasoline stocks, under such conditions that the gasoline produced therefrom has improved antiknock characteristics, a lowered sulfur content and other improved qualities.

Another object of my invention is a means for materially increasing the catalyst life and thereby effecting marked economies in the commercial practice of improving cracked gasoline stocksl by treatment with contact catalysts. Further objects will be apparent as the disclosure proceeds. This application is a continuation-in-part of my copending application Serial No. 106,698 illedv Cctober 20, 1936.

Referring to the drawing, which is a diagrammatic showing of an apparatus for carrying out the process of the invention, reference numeral I indicates a catalyst tower which encloses a catalyst bed. Raw gasoline vapors are admitted to the catalyst bed through conduit 2 and are ducting the overhead'vapors andffgas'esfto viurused for conducting the overhsadjto'af chemical treatingunit forsepiutingpiu'ified-l` gases for recycling through conduit! j LA suitable hydrocarbon gas; for examplemethane, alone or honed through branches lz'. heateri: isf interposed inline II for adding heatfto the'inert gasy when desired.` Suitable valves""are shown" l where needed to operate the apparatus in accord i ance with the invention.

I have 'found that in thetreatment ofcracked" gasoline stocks the' addition `0118ir Substantial pro- "j portion of so-called inert gases to tl'ievapors prior f to Contact with the catalyst has certaihdecmed advantages. These inerty gases servesomewhat as diluents of the hydrocarbon vapors 'being treated and lower`the percentage'fconcentration the vapors. t

The amount'of polymers formed from the unsaturated hydrocarbons when inert gases are added because of the low- .ered concentration of unsaturates in the vapors, l hence the degradation of polymeric "bodies to carbonaceous material and the like on and in the catalyst proceeds at a much reduced rate. Higher catalytic activity is, therefore, maintained over a much longer period o f time.

In the desulfurization of cracked gasoline stocks at temperatures in -the range of 500 to 800 F.. the equilibrium for thev decomposition of the organic 'sulfur compounds in cracked gasoline stocks to hydrogen sulilde has been found to be considerably more favorable when aj sub-v stantial proportion of inert'` gases is7 added lto the cracked gasolinevapors. The reaction, as exemplied by the aliphatic mercaptans. may be written asiollows: y t v cnHnmsH z2 Hrs .-1- can; Mercaptan hydrogen l olefin sulfide. 1

withdrawn at the bottom of the catalyst tower It is seen then that decreasing theconcentration `is` markedly `reduced oi olens favors more complete dissociation oi the mercaptans. This is of decided advantage `where the gasoline stock is high both in unsaturated hydrocarbons and in hydrogen sulfide. Lower temperatures can be used. and/or higher pressures, ii desired.

I have discovered too that the addition oi inert gases to the orackedgasoline vapors substantially, prevents the condensation of the high boiling components in the vapors from taking place when the vapors come into contact with the adsorbent catalytic material. In the processes used heretofore, the high boiling ends in cracked gasoline. pressure distillate or gas oil blends are condensed on the catalyst, thereby giving a liquid phase which aids and abets polymerization of unsaturated hydrocarbons, the polymers then poisoning the catalyst. To avoid this condensation, in certain instances superheating of the vapors above the normal treating temperature has been suggested. There are. however, certain disadvantages of such a superheating step, the principal one being that higher temperatures must be employed for treating and at such higher temperature cracking and/or polymerization proceeds at a higher rate, thereby tending to shorten catalyst life. In my process of adding inert gases to the petroleum vapors to avoid condensation of heavy ends on the catalyst, the temperature level needvnot be raised, in fact it may even be lowered somewhat, if desired. My process, therefore, permits taking the cracked gasoline vapors directly from the stills or the iractionating units and after adding the inert gases heated to the desired temperature, contacting the mixture with the catalyst.

I have found, too, that my present invention has decided advantages when treating gasoline` stocks in the vapor form at temperatures of about 900 to 1200 F. over contact catalysts such as bauxite, as disclosed in my application Serial No. 104,306, nled October 6, 1936. In the process described in this previous application, there are several concurrent reactions taking place among them being the dehydrogenation and rearrangement of certain of the hydrocarbon constituents of the vapors. This reaction is somewhat endothermic and in the operation of the process oftentimes a decided drop in temperature occurs within the catalyst bed, thereby retarding or stopping the reaction unless additional heat is provided by some means. If, however, my present invention is employed in this connection, l. e. adding a substantial proportion of inert gas to the vapors prior to treatment over the catalyst, then since the drop in temperature is proportional to the amount of hydrocarbonsk converted, the reduction in temperature will be proportionately less. In other words, a drop of 50 F. between the two ends of the catalyst bed may have no special disadvantages whereas a drop of 100 F. might render the process commercially inoperable. This drop in temperature can be brought by means of my present invention within any chosen temperature limits by varying the amount of inert gas to gasoline stock vapor. Instead of mixing the inert gases with the gasoline stock vapors prior to passage over the catalyst, if desired, the gases may be introduced into any particular section or part of the catalyst bed. The inert gases may also be heated to a temperature higher than the gasoline stock vapors, if desired, and in this Way supply a portion of the endothermic heat required in the reaction of the gasoline stock vapors. Therefore, these inert gases oier various means of controlling the temperature within desired limits.

I have found also that when an inert gas such as methane is added to the gasoline stock vapors prior to this treatment over a catalyst of the bauxite type at a temperature ot about 900 to 1200" F., and at a ilow rate oi-l to liquid volurnes per hour per volume of catalyst the dehydrogenation and rearrangement reactions involving certain of the hydrocarbon constituents are decidedly favorably influenced and a gasoline product withA superior antiknock qualities is lproduced. In the operation of this process high pressures are not needed, extremely good results being obtained in the range of atmospheric to 100 pounds per square inch.

Under the term of inert gases I mean those which do not undergo appreciable adverse change during the treating processes. For example, methane and/or the low boiling hydrocarbons constitutes a very desirable gas for the purposes enumerated. It is available around most -reilneries at an extremely low oost and it may be readily separated in the usual manner from the gasoline stock subsequent to the processing step. Hydrogen or hydrogen-bearing gases may be used if available at economic levels. The use of large percentages of such hydrogen gas may, however, innuence the dehydrogenation reactions to some extent. In such processes. methane may have certain additional advantages over hydrogen. Light gases formed in liquid or vapor phase cracking of heavy oils may likewise be used to advantage under certain conditions. Obviously other inert gases also may be employed. 'I'his inert gas, or any portion thereof, with or without treatment to remove hydrogen sulfide and the like, may be recycled, if desired.

A modification of this invention includes also the blending or mixing of gasoline stocks consisting principally of saturated hydrocarbons, e. g. natural and straight run gasolines, with gasoline stocks containing relatively high percentages of unsaturated hydrocarbons and readily polymerizable materials and then treating the mixture with the contact catalysts to reduce the sulfur content and improve the antiknock characteristics of the gasoline stocks. In this modlflcation of my invention the catalyst life is greatly prolonged and the overall improvement on the combined gasoline stocks is markedly increased. In one speciilc example, straight run gasoline and vapor recovery gasoline were treated in separate units over bauxite catalyst to remove a substantial proportion of the organic sulfur compounds which are so deleterious to octane number and lead response. After processing 1,000 barrels of each of these gasolines per ton of catalyst, a 50-50 blend was made from the composite products. This was compared with the product obtained by treating 1,000 barrelsof a 50-50 mixture of these gasolines per ton of catalyst under identical treating conditions. The desulfurized blend had a considerably lower sulfur content, a higher octane number and a greater lead response than the blended product made from the components desulfurized separately. The activity of the catalyst was not reduced nearly so fast by the blend as by the vapor recovery gasoline alone.

From the disclosure given herein, it is evident that inert gases also may be added to the blends of the various gasoline stocks as indicated above and additional advantages be obtained thereby. The ratio of inert gases to gasoline stock vapers may be varied over wide ranges, of course,

but in vgeneral to securel the maximum advantages the inert gases added to the vapors range v from to 'l5 per cent; depending on the gasoline stock being treated and on the conditions of treatment. Naturally, higher or lower quantities may be added and certain improvements be ob-` tained. i

Following treatment of the vapors through the catalyst the decomposed impurities and the inert gas may be removed in any 'conventional manner, as will be well understood by those skilled in the art.

The following example illustrates the benefi.

ciall effect obtained byadding methane gas to cracked gasoline stock vapors prior to treatment over bauxite catalyst.

' Cracked gasolinestock'vapors ata temperatureof 1000 F. were diluted with two volumes of passed over bauxite catalyst at a pressure of pounds per square inch gage and a ilow rate equivalent to two liquid volumes of the cracked methane gas at 100 F. and the mixture was then 'gasoline stock per hour per volume of .catalyst space. Thevapors leaving the catalyst chamber j were at a temperature of 980 F.v After the cata-4 .lytic treatment thelight gas and hydrogen sul-v 'de werevseparated from the gasoline hydrocarbons.. The composite gasoline from a 24-hour test run` showed an improvementl of 10 octane "numbers, and the vsulfur content was' reduced from'0g12 to 0.06 per cent. The activity of the catalyst at the end of the run was approximately v'75 per cent of the original activity.

1 `In a comparable run the cracked gasoline vabauxite catalyst under the same conditions of -pressure andcontact time asin the'previous test wherein methane was used as a diluent. In this vrun the vapors leaving the catalyst tower wereat a temperature o! 950 F., showing a drop of v50 while passing through the catalyst tower.

' t vporsat a temperature of 1000 F. were passed A35 without the addition of methane gas through The gasoline on the sameA throughput basis showed an improvement oi' only 6 octane numbers and the sulfur contentwas reduced from 0.12 to only 0.08 per cent. `The activity of the y catalyst at the end of the runvwas less than 'adsorbent clay at a temperature within the range of 500 to 1200 F., pressure between atmospheric and pounds andv at a flow rateof 1 to 100 liquid volumes per hour per volume of catalyst,

and controlling the temperature of the gasoline .stock vapor during the reaction by the addition of lan inert gas at a temperature abovethat of the gasoline stock vapors tov-supply a portion oi the endothermic heat of reaction. I o

2. In the process of treating cracked gasoline stocks over a bauxite catalyst at a temperature in the range of 500 to 1200 F. and pressure b e tween atmospheric and 100 pounds gage, the improvement comprising adding a substantial proportion of 'a straight run gasoline stock to thev cracked gasoline stock prior to the catalytic treatment to decrease the rate of poisoning and to prolong the life of the catalyst, and controlling the temperature of the gasoline stock vapor during the reaction by the addition of an inert gas at a temperature above that of the gasoline stock vapors to supply a portion of the eny dothermic heat of reaction.

WALTER AQscHULzE. 

